Reaction products of nitriles



Patented Oct. 28, I 1952 REACTION PRODUCTS F NITRILES v Ernst Zerner andMark W. Pollock, New York, N. Y., assignors to Sun Chemical Corporation,I New York, N. Y., a corporation of Delaware..-

No Drawing. Application June 10, 1948, Serial No. 32,263

7 Claims. I

This invention relates to new organic materials.

In a copending application, Serial No. 16,135 filed March 20, 1948,there are described and claimed hexahydro-1,3,5-triacy1-s-triazinematerials represented by the general formula R (i=0 i where R representssubstituted or unsubstituted open chain hydrocarbon radicals. One of thematerials described in the above identified copending application ishexahydro-l,3,5-triacrylyl s-triazine. Also there is described in thiscopending application hexahydro 1,3,5 trimethacrylyl-s-triazine.

We have found according to the present invention that certain new anduseful products may be obtained by proper further reactions with thelatter materials.

The above derivatives of triazines contain in their molecular structurethree vinyl groupings. In accordance with the present inventionderivatives are secured by reactions which lead, by the formation ofaddition compounds to saturation of one, two or three of the vinylgroups present. Such products may be described by'the formula Il a 1 N oRi- N N- -R 0 H2 wherein R3 is a radical which is selected from thegroup consisting of -CA=CHA where A is selected from the groupconsisting of hydrogen, halogen and lower alkyl radicals and additionproducts of CA=Cl-IA and where R4 is an addition product of CA=CHA.

Of these materials those which contain one or two vinyl groups presentin the molecule of the products may be further treated to efiectpolymerization of this material, either alone or admixed with otherpolymerizable monomers to furnish valuable resinous materials which maybe 2 employed in various arts in which such materials find application,for instance, as coating materials for paper, wood, metal and cloth, inconjunction with drying oils, and the like.

The polymerized materials, described and claimed in a copendingapplication Serial No.

32,264 filed on even date herewith in the names of Ernst Zerner, MarcelGradsten, and Fred W. West may be described as polymerization productsof compounds of the general formula R1 1 i=0 l: HZC/ oH,

o o R, N N-(i-Ra where R1 represents the radical -CA=CH2 wherein A isselected from the group consisting of hydrogen, halogen and lower alkylradicals and where R2 is a radical selected from the group consisting ofCA=CH2 and addition products of CA=CH2. I

As described in the above identified copending application Serial No.16,135, hexahydro-1,3,5- triacrylyl-s-triazine satisfactorily may beprepared as follows: In a suitable reaction vessel provided with astirrer, reflux condenser, thermometer and a dropping funnel are placed265 parts'by weight of acrylonitrile dissolved in 400 parts by weight ofbenzene, together with 2.8 parts of concentrated sulfuric acid. In thedropping funnel is placed a solution of parts by weight of trioxanedissolved in 400 parts by weight of benzene. The acrylonitrile solutionis warmed, satisfactorily on a boiling water bath, and the material inthe dropping funnel added at a rate such that the mixture is maintainedunder reflux condition. When all of the solution in the dropping funnelhas been added, the resulting admixture is heated under refluxconditions for an additional period of approximately three hours.Subsequently the mixture, which contains a yellow precipitate, isallowed to stand overnight and the precipitate then separated byfiltration and subsequently recrystallized from ethanol. I

As described in the above identified copending application, Serial No.16,135, similar products may be obtained using as starting materialsnitriles such as methacrylonitrile, alpha chloracrylonitrile and similarnitriles containing a vinyl'group.

In place of the individual nitriles, mixtures of nitrile materials canbe employed.

Triazines of the above type and containing three vinyl groups may berepresented by the formula OH; in 6:0 it

1120 CHz.

where A is hydrogen, halogen or a lower-alkyl. radical. Such materialsmay be subjected to polymerization reactions either alone or admixedwith other polymerizable monomers to form valuable resinousreactionproductsa Illustrative of the preparation of: such; polymermaterials are thefollowing examples:

ExampZePI A'solution containing 6 per*cent ffhexahydro- 1,3; triacrylyls-triazine in per cent acetic acid isheate'd to boiling; Uponzsuch heattreatment a polymer material is precipitatedsi from solution and may beseparated therefrom for further utilization.

In the above preparation the rate of formation of the polymer materialcan be increased by utilization of a peroxide in the reaction solution.

Eimmpl'e A 5 per cent-solution of-hexahydro-lBfi-triacrylyl-s-triazinein chloroform together with 0.1 per cent of benzoyl peroxide, based onthe tri-. azine; iswarmed to; efiect evaporation or. the chloroform-andsubsequently heated-for a'period ofaapproximately /z:hour at atemperature of 130 0.21m asuitab1e container... A brittle.white;..insoluble :polymermateria l .is:.secured;.

Polymerization of such materials; may; also be efiected; for: example;in: the: presence ofa; textile material in which case a product. issobtained which: comprises 'thetextile materialimpregnatemwiththeresinous product..-

Also. :as above set. forth, copolymerizationunay be=eiiected; asillustratively. set-1 fortl-nin the following example.

Ami-xture containing .99.65-Iper..cent by weight of styrene, 0.25 percent by weight-ofhex'ahydro- 1,3,5 triacrylyl-s-triazine and .0.1percent of henzoyl-peroxide is heated to 60 C. to .eifectiormation ofapolymermaterial.. merization much morerapidv with. the .triazinepresent: their in its absence. and. theproduct ob.- tained -isa crosslinked polymer, as distinguished fromlinearv polymerswhichare. obtained.by. the polymerization of.'styrene.. Evidence forv this is i the factthat the. copolymerization productisinsoluble in xylol,. whereaspolymers. of Tstyreneare solublein. such solvent.

Another. aspect is 'theipreparation. .ofIaddition products of triazines.of the type. described above iniwhich. one, twoori three of-Ithe'vinyl'groups presentare converted intosaturated. groupings byrsuitablereaction. A variety of 'difierentmaterials can be employed .to.reactwith the .vinyl The: rate ofqpolygroups presentin the triazinesto'add 'th'eretoand some of the materials which will react are compoundssuch as sodium bisulfite, alcohols, halogens, conjugated dioleflns,amines, compounds having an active hydrogen, hydrogen sulfide andmercaptans.

Where theabove illustrative materials are employed toefiectreactionwithtriazines containing vinyl groups, either one, two or three of the vinylgroups may be saturated, depending upon the amount of reactin materialsutilized. Where only one or'two of the vinyl groups is thussaturated...the. resultingmaterial may be polymerized .eitherialoneiorin conjunction with other polymeriz-able' monomers to form a resinousproduct, Whose characteristics will be dependent in partiupon'the"modifying reacting material employed to effect saturation of the vinylgroupings priorto polymerization, as described and claimed in the saidcopending application Serial No. 32,284 filed on even. dateherewith.

Illustrativeexamples.settinggforth. thisv aspect include-the.following.-

Eztample IV 20 parts by weight. of hexahydro-1,3,5-triacrylyl-s-triazineis dissolved in 500 parts of water at approximately 75 C. When solutionis completed there is added thereto 82 parts by weight of sodiumbisulfite. which corresponds to one molecular equivalent of sodiumbisulfite per mol of triazine.' Addition .of the bisulflte is effectedwhile maintaining the solution under agitation conditions. When additionof the bisulfite is completed the admixture is cooled and may befiltered to remove traces. of impurities. Aslightly milky.solutionresults. Upon drying of this solutionnnder.vacuum conditions,-thereis obtained a clear-white= solid, which: iseasily solublein waterand. which doesvnot melt. or decompose .at temperatures up to 250. C.

Example V' Aqueous solutions. of the product aofExample IV,upontreatment with. 30. per cent hydrogen peroxide solution polymerizedto. givea resinous product.-

EmampZe'VI A5 6 per centsolutionofthe product ofExample IV inwater,together. with. two dropsof 30 .per cent. hydrogenperoxide per. parts byweight of solution .washeatedat boiling. for. tenminutes. The resultingsolution was cooled and was employed in normal padding operation toeiTect impregnation of percale.- After padding was completed, theimpregnated percale was dried at 100 C. The treated materialwasremarkably stiiier than the original untreatedgoods, such efiect beingcaused by the polymerization of the sodium bisulfite addition product ofhexahydro-l,3,5-triacrylyl-s-triazine in situ in the fabric material.

Example VII 20 parts .by weight of hexahydro-l,3,5-triacrylyl-s-triazineis dissolved in 500 parts of weight ofwater at 75 C. When solution iscompleted there is added, with agitation, 16.4 parts by weight of'sodiumbisulfite corresponding to two molecular equivalents of sodium bisulfiteper mol of. tria'zine. After addition of the bisulfite is completed, theadmixture is cooled and filtered'to remove impurities. Upondrying ofthefiltrate under vacuum condition; a clear whitewatersoluble'product'is secured which does not melt at temperaturesupto' 250"C;

Example VI I] Polymerization of the product of Example VII is obtainedby dissolving the product in water and treating the aqueous solutionwith per cent hydrogen peroxide.

Example IX Hexahydro-1,3,5-triacrylyls-triazine is treated as describedin Example VII except that there is used 24.6 parts by weight ofsodiumbisulfite corresponding to three molecular equivalents of sodiumbisulfite per mol of triazine. A water soluble product is secured whichdoes not underso polymerization.

Example X 10 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine isdissolved in'200 parts of chloroform in a reaction vessel equipped withstirring,

device, thermometer, dropping funnel and reflux condenser. There is thenadded drop-wise a solution of 0.4 part by weight of metallic sodiumdissolved in 12 parts of n-butanol. Upon completion of this addition theadmixture is stirred for a length of time sufiicient to complete thereacwith sodium sulfate, and then filtered. To remove ether theadmixture is distilled under "reduced pressure. A brown viscous oil, thebutyl alcohol addition product of hexahydro-1,3,5triacrylyl-s-triazineis obtained.

The product, upon heating together with benzoyl peroxide, forms aresinous product.

Hexahydro-1,3,5-triacrylyl-s-triazine may be chlorinated by bubblingchlorine into the material in the presence of a small amount of apolymerization inhibitor such as hydroquinone in an amount sufiicient toeffect saturation of one, two or three of the vinyl groups present. Thecourse of the reaction may be determined by the increase in weight ofthe reaction admixture at intervals. Where chlorination is discontinuedat a point where less than all of the vinyl groups are saturated, aproduct is obtained which may be polymerized. Polymerizationsatisfactorily '6 ture is warmed until solution'is completed, thencooled to room temperature and there is then added thereto, in smallportions. 8 parts by 2-. weight of decyl amine at a'rate such that theis effected in the presence of a peroxide polymerization catalyst.

' Example x1 Example XII In a suitable reaction vessel were placed partsof chloroform and 12.5 parts by weight ofhexahydro-1,3,5-triacrylyl-s-triazine. The mix- 1 temperature of theadmixture does not rise above approximately 37 C. After addition of theamine is completed, the reaction admixture is stirred for a period oftime sufficient toinsure completion of the reaction which with thequantitles above described is approximately 1.25 hours. The mixture thenmay be allowed to stand for several hours and subsequently is filteredand the chloroform removed therefrom by distillation under reducedpressure. A clear viscous liquid material is obtained.

Example XIII Polymerization of the product of Example XII may be securedeither in the presence of a peroxide oxidation catalyst or, inthe'absence of a catalyst, over a somewhat longer period of time. Theproduct which is obtained by polymerization is insoluble in ordinaryorganic solvents indicating that the process of polymerization includescross-linking of the polymers and that the product is not a. simplelinear polymer.

Example XIV Following the procedure described in Example 1G1 andutilizing 16' parts by weight of decyl amine there is secured anaddition product in which two of the three vinyl groups of the triazineshave been saturated. This product polymerizes at a rate slower than theproduct of EX- ample XIII and serves satisfactorily. as a plasticizingpolymer to be used in conjunction with the polymer of Example XIII.

Example XV In a reaction vessel are placed 50 parts of chloroform and12.5 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine and thereis then added thereto. with stirring 3.65 parts by weight of diethylamine dissolved in 10 parts of chloroform. After the addition has beencompleted, the admixture is stirred for approximately 2 hours, stirringthen discontinued and the mixture allowed to stand for several hours. Itthen is filtered and the filtrate evaporated under reduced pressure toremove the chloroform. A white solid product is obtained which may becrystallizedfrom ethanol to give a product which softens at C. and meltsat 0'. Recrystallization of this product from'toluene gives a materialwhich softens at 146 C. and melts at 149 C.

The product of this reaction, which has only one of the vinyl groups ofthe triazine saturated, is polymerizable under the general conditionsset forth in previous examples.

EmampleXVI The procedure described in Example XV is followed except thatthere is used 8 parts by weight of diethyl amine to give a product whichI is an addition product containing two molecular equivalents of diethylamine per mol of triazine. The product is water-soluble and is a surfaceactive material.

Example XVII The procedure described in Example XV is followed exceptthat there is utilized 12 parts by weight of diethyl amine to give areaction product containing three molecular equivalents of diethyl amineper mol of triazine.

materials such as hydrogen sulfide are set forth in U. S. ,P, No.2,163,176 dated June 20, 1939.

While the above described products constitute preferred embodiments ofthe invention, changes may be made therein without departing from thescope of the invention, as defined in the appended claims.

'What is claimed is: 1. As new products, compounds of the .formula whereA is selected from the group consisting of hydrogen, halogen and loweralkyl radicals, and where Y is selected from the group consisting ofSOs-alkali metal, oxy-alkyl, and amino-.alkyl radicals.

2. As a new product. a compound of the formula CH: l'm

o 1LT HQC \CE;

1; o CHFC-J-N )ir-iLoHr-oHT-Y where 'Y represents an amino-alkylradical.

3. As a new product, a compound of formula the where Y represents anamino-alkyl radical.

4. As a new product, a compound of the formula where Y represents anamino-.alkyl radical.

5. As a new product, a compound of the formula CH; n 1

6. As a new product, a compound of the formula 7. As a new product, acompound of the formula 0 l N-F-CHr-CHr-S OaNa ERNST ZERNER. MARK W.'POLLOCK.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,989,042 Kimz Jan. 22, 19.352,115,550 Ellis Apr. 26, .1938 2,304,624 Burke Dec. 8, 1942 2,321,989Burke June 15, 1945

1. AS NEW PRODUCTS, COMPOUND OF THE FORMULA